Functionalized poly(aryl ether sulfones) copolymers

Abstract

The invention relates to a side-chain functionalized copolymer (P1) and to the process for preparing the side-chain functionalized copolymer (P1). The present invention also relates to the use of the copolymer (P1) in the preparation of a membrane, a composite material or a coating.

The invention claimed is: 
     
       1. A copolymer (P1) comprising:
 recurring units (R P1 ) of formula (M): 
 
       
         
           
           
               
               
           
         
         recurring units (R* P1 ) of formula (N): 
       
       
         
           
           
               
               
           
         
       
       wherein
 each R 1  is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; 
 each i is independently selected from 0 to 4; 
 T is selected from the group consisting of a bond, —CH 2 —; —O—; —SO 2 —; —S—; —C(O)—; —C(CH 3 ) 2 —; —C(CF 3 ) 2 —; —C(═CCl 2 )—; —C(CH 3 )(CH 2 CH 2 COOH)—; —N═N—; —R a C═CR b —, where each R a  and R b , independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH 2 ) m — and —(CF 2 ) m — with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof; 
 G N  is selected from the group consisting of at least one of the following formulas formulae: 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         each k is independently selected from 0 to 4; 
         each j is independently selected from 3 to 7; 
         each R 2  is independently selected from the group consisting of: 
         (CH 2 ) u —COOH, with u being selected from 1 to 5, 
         (CH 2 ) k —OH, with k being selected from 1 to 5, 
         (CH 2 ) p —NR a R b , with p being selected from 1 to 5, and R a  and R b  being independently a C1-C6 alkyl or H, with the proviso that R a  and R b  are not both CH 3 , 
         (CH 2 )q-SO 3 Na, with q being selected from 1 to 5, 
         (CH 2 )a-COCH 3 , with a being selected from 0 to 10 
         (CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5, 
         (CH 2 )s-(CF 2 )t-CF 3 , with s being selected from 1 to 5 and t being selected from 1 to 10, 
         CO—R c , with R c  being a C1-C6 alkyl or H, 
         (CH 2 )v-CH 3 , with v being selected from 5 to 30, and 
         (CH 2 )w-Ar, with w being selected from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings. 
       
     
     
       2. The copolymer (P1) of  claim 1 , wherein T in recurring units (R P1 ) is selected from the group consisting of a bond, —SO 2 — and —C(CH 3 ) 2 —. 
     
     
       3. The copolymer (P1) of  claim 1 , wherein i is zero for each R 1  of recurring units (R P1 ) and recurring units (R* P1 ). 
     
     
       4. The copolymer (P1) of  claim 1 , wherein k is 0 and j is 3 in recurring units (R* P1 ). 
     
     
       5. The copolymer (P1) of  claim 1 , wherein the molar ratio of recurring units (R P1 )/recurring units (R* P1 ) varies between 0.01/100 and 100/0.01. 
     
     
       6. The copolymer (P1) of  claim 1 , wherein recurring units (R P1 ) are according to formula (M1): 
       
         
           
           
               
               
           
         
       
     
     
       7. The copolymer (P1) of  claim 1 , wherein R 2  in formulae (G N1 ), (G N2 ), (G N3 ), (G N4 ), (G N5 ) or (G N6 ) is independently selected from the group consisting of:
 CH 2 —COOH, 
 (CH 2 ) 2 —OH, 
 (CH 2 ) 2 —NH 2 , 
 (CH 2 ) 3 —SO 3 Na, 
 (CH 2 ) 3 —Si(OCH 3 ) 3 , 
 (CH 2 ) 2 —(CF 2 ) 7 —CF 3 , 
 C═O—H, 
 (CH 2 ) 9 —CH 3 , 
 CH 2 -Ph, with Ph being benzene. 
 
     
     
       8. The copolymer (P1) of  claim 1 , comprising collectively at least 50 mol. % of recurring units (R P1 ) and (R* P1 ), based on the total number of moles in the copolymer (P1). 
     
     
       9. A process for preparing copolymer (P1) comprising reacting in a solvent a copolymer (P0) comprising:
 recurring units (R P0 ) of formula (M): 
 
       
         
           
           
               
               
           
         
         recurring units (R* P0 ) of formula (P): 
       
       
         
           
           
               
               
           
         
         
           wherein
 each R 1  is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; 
 each i is independently selected from 0 to 4; 
 T is selected from the group consisting of a bond, —CH 2 —; —O—; —SO 2 —; —S—; —C(O)—; —C(CH 3 ) 2 —; —C(CF 3 ) 2 —; —C(═CCl 2 )—; —C(CH 3 )(CH 2 CH 2 COOH)—; —N═N—; —R a C═CR b —, where each R a  and R b , independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH 2 ) m — and —(CF 2 ) m — with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof, 
 G P  is selected from the group consisting of at least one of the following formulae: 
 
         
       
       
         
           
           
               
               
           
         
         
           
             each k is independently selected from 0 to 4, with a compound of formula (I): R 2 —SH 
           
           wherein R 2  is selected from the group consisting of:
 (CH 2 )u-COOH, with u being selected from 1 to 5, 
 (CH 2 )k-OH, with k being selected from 1 to 5, 
 (CH 2 )p-NR a R b , with p being selected from 1 to 5, and R a  and R b  being independently a C1-C6 alkyl or H, with the proviso that R a  and R b  cannot be are not both CH 3 , 
 (CH 2 )q-SO 3 Na, with q being selected from 1 to 5, 
 (CH 2 )a-COCH 3 , with a being selected from 0 to 10 
 (CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5, 
 (CH 2 )s-(CF 2 )t-CF 3 , with s being selected from 1 to 5 and t being selected from 1 to 10, 
 CO—R c , with R c  being a C1-C6 alkyl or H, 
 (CH 2 )v-CH 3 , with v being selected from 5 to 30, and 
 (CH 2 )w-Ar, with w being selected from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings, 
 
         
       
       wherein the molar ratio of compound (I)/polymer (P0) varies between 0.01/100 and 100/0.01, at a temperature ranging from 10° C. and 300° C. 
     
     
       10. The process of  claim 9 , being carried out in a solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole, chloroform, dichloromethane (DCM) and sulfolane. 
     
     
       11. The process of  claim 9 , being carried out in the presence of:
 at least one free radical initiator, and/or 
 at least one catalyst. 
 
     
     
       12. The process of  claim 9 , being carried out in the presence of a base. 
     
     
       13. The process of  claim 9 , being carried out by exposing the reaction mixture to UV light at a wavelength ranging from 300 nm to 600 nm. 
     
     
       14. The process of  claim 9 , wherein the functionalized PAES copolymer (P0) comprises collectively at least 50 mol. % of recurring units (R P0 ) and (R* P0 ), based on the total number of moles in the copolymer (P0). 
     
     
       15. The process of  claim 9 , wherein the functionalized PAES copolymer (P0) is prepared by condensation of at least one aromatic dihydroxy monomer (a1), with at least one aromatic sulfone monomer (a2) comprising at least two halogen substituents at at least one allyl-substituted aromatic dihydroxy monomer (a3). 
     
     
       16. A method for preparing a membrane, a composite material or a coating, comprising using the copolymer of  claim 1 . 
     
     
       17. The process of  claim 11 , being carried out in the presence of:
 2,2′-Azobis(2-methylpropionitrile) (AIBN) as at least one free radical initiator, and/or 
 at least one catalyst selected from peroxides and hydroperoxides. 
 
     
     
       18. The process of  claim 12 , wherein the base is selected from the group consisting of N-Ethyl-N-(propan-2-yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine. 
     
     
       19. The copolymer (P1) of  claim 1 , wherein the molar ratio of recurring units (R P1 )/recurring units (R* P1 ) varies between 1/1 and 12/1.